Polyester plasticizer and chlorine-containing resin compositions

ABSTRACT

A polyester plasticizer which is obtained by reacting a diol component (a) consisting of 100 parts by mole of 2-methyl-1,3-propanediol, 10 to 1000 parts by mole of 3-methyl-1,5-pentanediol and 0 to 1000 parts by mole of other aliphatic diol with an organic dicarboxylic acid components (b) consisting of 100 parts by mole of adipic acid and 0 to 100 parts by mole of other organic dicarboxylic acid and a chain terminator (c) consisting of a monovalent aliphatic alcohol or a monovalent aliphatic organic acid and which has an average molecular weight of 500 to 5000. This plasticizer is excellent in plasticizing efficiency and can impart excellent oil resistance to synthetic resins such as chlorine-containing resins.

TECHNICAL FIELD

The present invention relates to a specific polyester plasticizer and achlorine-containing resin composition that contains the plasticizer.More particularly, it relates to a polyester plasticizer obtained by thereaction of a diol component essentially containing2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol, an organicdicarboxylic acid component essentially containing adipic acid, and achain terminator, and to a chlorine-containing resin composition thatcontains the plasticizer.

BACKGROUND ART

Polyester compounds obtained from aliphatic diols and aliphaticdicarboxylic acids are useful as plasticizers for synthetic resins andhave been widely applied particularly to chlorine-containing resins,such as vinyl chloride resins.

A polyester plasticizer providing improved low temperature flexibilitythat is prepared by using 2-methyl-1,3-propanediol as an aliphatic diolis disclosed in JP-A-61-78827. However, the proposed polyesterplasticizer has low plasticization efficiency and fails to impartsufficient oil resistance to chlorine-containing resins.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a polyester plasticizersuperior in plasticization efficiency and capable of imparting high oilresistance to synthetic resins, such as chlorine-containing resins, anda chlorine-containing resin composition containing the polyesterplasticizer.

As a result of extensive investigations, the present inventors havefound that the above object of the invention is accomplished by apolyester compound obtained from specific materials.

Having been reached based on the above finding, the present inventionprovides a polyester plasticizer having an average molecular weight of500 to 5000 which is obtained by the reaction of (a) a diol componentcomprising 100 molar parts of 2-methyl-1,3-propanediol, 10 to 1000 molarparts of 3-methyl-1,5-pentanediol, and 0 to 1000 molar parts of anadditional aliphatic diol, (b) an organic dicarboxylic acid componentcomprising 100 molar parts of adipic acid and 0 to 100 molar parts of anadditional organic dicarboxylic acid, and (c) a chain terminatorcomprising a monovalent aliphatic alcohol or a monovalent aliphaticorganic acid.

The present invention also provides a chlorine-containing resincomposition comprising 100 parts by mass of a chlorine-containing resin,10 to 100 parts by mass of the polyester plasticizer, and 0 to 100 partsby mass of other additives.

BEST MODE FOR CARRYING OUT THE INVENTION

The modes for carrying out the present invention will be described indetail.

The polyester plasticizer of the present invention is obtained byallowing to react (a) a diol component, (b) an organic dicarboxylic acidcomponent, and (c) a chain terminator.

The diol component (a) is an aliphatic diol mixture containing2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol as essentialcomponents and optionally containing other aliphatic diols.

The other aliphatic diols include ethylene glycol, 1,2-propanediol,1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol,neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol,1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol,2-methyl-1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

The proportion of 3-methyl-1,5-pentanediol in the diol component (a) is10 to 1000 molar parts, preferably 10 to 200 molar parts, stillpreferably 20 to 100 molar parts, per 100molar parts of2-methyl-1,3-propanediol. If the proportion is less than 10 molar parts,sufficient low temperature flexibility is not assured. Use of more than1000 molar parts impairs the oil resistance.

The amount of the other aliphatic diols in the diol component (a) is 0to 1000 molar parts, preferably 0 to 500 molar parts, still preferably 0to 200 molar parts, per 100 molar parts of 2-methyl-1,3-propanediol. Ifthe amount exceeds 1000 molar parts, high plasticization efficiency andexcellent oil resistance are not secured.

The organic dicarboxylic acid component (b) contains adipic acid as anessential component and other organic dicarboxylic acids as an optionalcomponent(s).

The other organic dicarboxylic acids include aliphatic dicarboxylicacids, such as oxalic acid, malonic acid, succinic acid, glutaric acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioicacid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid,3-methylpentanedioic acid, 2-methyloctanedioic acid,3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, and ahydrogenated dimer acid; aromatic dicarboxylic acids, such as phthalicacid, terephthalic acid, isophthalic acid, orthophthalic acid, andnaphthalenedicarboxylic acid; and alicyclic dicarboxylic acids, such as1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid,1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, and1,4-dicarboxylmethylenecyclohexane.

The other organic carboxylic acids can be used in an amount of 0 to 100molar parts, preferably 0 to 50 molar parts, still preferably 0 to 20molar parts, per 100 molar parts of adipic acid. If the amount exceeds100 molar parts, high plasticization efficiency and excellent oilresistance are not assured.

The chain terminator (c) comprises a monovalent aliphatic alcohol or amonovalent aliphatic organic acid. Examples of the aliphatic alcohol aremethanol, ethanol, 1-propanol, 2-propanol, butanol, 2-butanol, isobutylalcohol, tert-butyl alcohol, amyl alcohol, hexanol, isohexanol,heptanol, 2-heptanol, octanol, isooctanol, 2-ethylhexanol, nonanol,isononanol, decanol, isodecanol, undecanol, isoundecanol, dodecanol,benzyl alcohol, 2-butyloctanol, 2-butyldecanol, 2-hexyloctanol,2-hexyldecanol, stearyl alcohol, 2-octyldecanol, 2-hexyldodecanol,2-octyldodecanol, 2-decyltetradecanol, tridecyl alcohol, and isotridecylalcohol. These compounds can be used either individually or as a mixtureof two or more thereof.

The monovalent aliphatic organic acid includes formic acid, acetic acid,propionic acid, butyric acid, isobutyric acid, valeric acid, caproicacid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid,neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid,myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearicacid, and coconut oil fatty acid. These compounds can be used eitherindividually or as a mixture of two or more thereof.

The polyester plasticizer of the present invention that is obtained byallowing to react the diol component (a), the organic dicarboxylic acidcomponent (b), and the chain terminator (c) has an average molecularweight of 500 to 5000, preferably 500 to 3000, still preferably 1000 to3000. If the molecular weight is smaller than 500, the plasticizerinvites such problems as volatilization, bleed out, and migration. Ifthe molecular weight is greater than 5000, compatibility and flexibilitydeteriorate.

The viscosity of the polyester plasticizer according to the invention isnot particularly limited and arbitrarily adjustable according to theintended use and the method of use. For application to achlorine-containing resin, the polyester plasticizer of the presentinvention usually has a viscosity of 100 to 5000 mPa.s and preferablyhas an acid value of 1 or smaller and a hydroxyl value of 30 or smaller.

The manner of allowing the diol component (a), the organic dicarboxylicacid component (b), and the chain terminator (c) to react with eachother to produce the polyester plasticizer of the invention is notparticularly restricted. Well-known processes for producing polyesterplasticizers can be applied. Such processes include (i) directcondensation between the diol and the organic dicarboxylic acidcomponents, (ii) ester interchange between the diol and a lower alkylester of the organic carboxylic acid, and (iii) condensation between thediol and a halide of the organic carboxylic acid. These reactions can becarried out either in the absence or presence of a catalyst foresterification. The chain terminator (c) participates in the reactionthrough a similar esterification reaction. The molar ratio of the diolcomponent (a), the organic dicarboxylic acid component (b), and thechain terminator (c) is arbitrarily decided so as to result in amolecular weight of 500 to 5000.

The esterification catalyst includes acid catalysts, such as sulfuricacid, phosphoric acid, zinc chloride, benzenesulfonic acid,p-toluenesulfonic acid, and 4-chlorobenzenesulfonic acid; titaniumalkoxides, such as titanium tetramethoxide, titanium tetraethoxide, andtitanium tetraisopropoxide; acylated titanium compounds, such aspolyhydroxytitanium stearate and polyisopropoxytitanium stearate;titanium chelate compounds, such as titanium acetylacetate, titaniumtriethanolamine, titanium ammonium lactate, titanium ethyl lactate, andtitanium octylene glycolate; tin compounds, such as dibutyltindilaurate, dibutyltin oxide, and dibutyltin diacetate; metal acetates,such as magnesium acetate, calcium acetate, and zinc acetate; and metaloxides, such as antimony oxide and zirconium oxide. These catalysts canbe used either individually or as a combination thereof.

If desired, the polyester plasticizer of the present invention may beobtained by using other materials in addition to the diol component (a),the organic dicarboxylic acid component (b), and the chain terminator(c). Usable other materials include hydroxy acids, such as12-hydroxystearic acid, poly(12-hydroxystearic acid), 4-hydroxybenzoicacid, and poly(4-hydroxybenzoic acid); tri- or higher n-hydric alcohols,such as trimethylolethane, trimethylolpropane, hexitols, pentitols,glycerol, polyglycerol, pentaerythritol, dipentaerythritol, andtetramethylolpropane; and tricarboxylic acids, such as trimellitic acidand trimesic acid. The other materials are preferably used in a totalamount of 10 molar parts or less per 100 molar parts of the total of thediol component (a), the organic dicarboxylic acid component (b), and thechain terminator (c).

The polyester plasticizer according to the present invention ispreferably used for synthetic resins, particularly chlorine-containingresins.

The chlorine-containing resin composition according to the presentinvention comprises 100 parts by mass of a chlorine-containing resin, 10to 100 parts by mass of the polyester plasticizer of the presentinvention, and 0 to 100 parts by mass of other additives.

The chlorine-containing resin includes polyvinyl chloride, chlorinatedpolyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylenecopolymers, vinyl chloride-propylene copolymers, vinyl chloride-styrenecopolymers, vinyl chloride-isobutylene copolymer, vinylchloride-vinylidene chloride copolymers, vinyl chloride-styrene-maleicanhydride terpolymers, vinyl chloride-styrene-acrylonitrile terpolymers,vinyl chloride-butadiene copolymers, vinyl chloride-isoprene copolymers,vinyl chloride-chlorinated propylene copolymers, vinylchloride-vinylidene chloride-vinyl acetate terpolymers, vinylchloride-maleic ester copolymers, vinyl chloride-methacrylic estercopolymers, vinyl chloride-acrylonitrile copolymers, vinylchloride-vinyl ether copolymers, and mixtures of two or more thereofFurther included are mixtures of these chlorine-containing resins andchlorine-free synthetic resins, such as acrylonitrile-styrenecopolymers, acrylonitrile-styrene-butadiene terpolymers, ethylene-vinylacetate copolymers, ethylene-ethyl(meth)acrylate copolymers, andpolyesters, and block and graft copolymers composed of thechlorine-containing resin units and the chlorine-free resin units.

The amount of the polyester plasticizer in the chlorine-containing resincomposition is such that can impart flexibility required for particularuse to the resin. It is usually 10 to 100 parts by mass per 100 parts bymass of the chlorine-containing resin.

The other additives include commonly known ones, such as plasticizersother than the polyester plasticizers of the present invention,β-diketone compounds, electrical insulation improvers, various metalsalts, polyols, epoxy compounds, organic phosphite compounds, phenol orsulfur antioxidants, ultraviolet absorbers, hindered amine lightstabilizers, inorganic stabilizers, fillers, anti-fogging agents,anti-misting agents, stabilization assistants, and organotin compounds.

The plasticizers other than the polyester plasticizers of the presentinvention include phthalic acid plasticizers, such as dibutyl phthalate,butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononylphthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexylphthalate, and dioctyl terephthalate; adipic acid plasticizers, such asdioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol)adipate; tetrahydrophthalic acid plasticizers, azelaic acidplasticizers, sebacic acid plasticizers, stearic acid plasticizers,citric acid plasticizers, trimellitic acid plasticizers, pyromelliticacid plasticizers, and biphenylene polycarboxylic acid plasticizers. Theamount of these plasticizers is preferably not more than 100 parts bymass per 100 parts by mass of the polyester plasticizer of the presentinvention.

The β-diketone compounds include dibenzoylmethane, benzoylacetone,stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid,tribenzoylmethane, 1,3-bis(benzoylacetyl)benzene, and their metal salts(e.g., salts with lithium, sodium, potassium, calcium, magnesium, bariumor zinc). The amount of the β-diketone compound to be added preferablyranges from 0.01 to 10 parts by mass per 100 parts by mass of thechlorine-containing resin. Amounts less than 0.01 part by mass produceinsubstantial effects of addition. Addition of more than 10 parts bymass brings about no further improvement and can reduce heat resistance.

The electrical insulation improvers include those disclosed inJP-A-57-177040, JP-A-5-262943, JP-A-5-179090, and JP-A-9-324089, i.e.,amorphous calcium silicate (hydrate), a composition containingα-dicalcium silicate hydrate and calcium hydroxide, and a silicate ofaluminum or an alkaline earth metal. Preferred of them is amorphouscalcium silicate (hydrate) for its superiority in insulation performanceand heat resistance.

The amorphous calcium silicate (hydrate) includes tobermorite gel, C—S—H(I), and C—S—H (II). The amount of the amorphous calcium silicate(hydrate) to be added is preferably 0.001 to 3 parts by mass, stillpreferably 0.01 to 1 part by mass, per 100 parts by mass of thechlorine-containing resin. An amount less than 0.001 part by mass islittle effective. Addition of more than 3 parts by mass can result inreduction of heat resistance or coloration.

The metal salts as an additive include metal (e.g., Li, Na, K, Ca, Ba,Mg, Sr, Zn, Cd, Sn, Cs, Al or organotin) salts of organic acids orphenols and metal (e.g., Li, Na, K, Ca, Ba, Mg, Sr, Cd, Sn, Cs, Al ororganotin) salts of organic phosphoric acids. A preferred amount of themetal salt to be added is 0.05 to 10 parts by mass per 100 parts by massof the chlorine-containing resin.

The organic acids of the metal salts include caproic acid, caprylicacid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoicacid, undecylenic acid, lauric acid, myristic acid, palmitic acid,stearic acid, isostearic acid, 12-hydroxystearic acid, chlorostearicacid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleicacid, linolenic acid, oleic acid, arachic acid, behenic acid, erucicacid, brassidic acid, and like acids; naturally occurring mixtures ofthe above-recited organic acids, such as animal fat fatty acids, coconutoil fatty acid, tung oil fatty acid, soybean oil fatty acid, and cottonseed oil fatty acid; benzoic acid, p-tert-butylbenzoic acid,ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylylic acid,salicylic acid, 5-tert-octylsalicylic acid, naphthoic acid,cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, andmethacrylic acid. The phenols of the metal salts include phenol, cresol,ethylphenol, cyclohexylphenol, nonylphenol, and laurylphenol. Theorganic phosphoric acids of the metal salts include mono- ordioctylphosphoric acid, mono- or dilaurylphosphoric acid, mono- ordistearylphosphoric acid, mono- or di(nonylphenyl)phosphoric acid,nonylphenyl phosphonate, and stearyl phosphonate.

Of these metal salts preferred are organic acid zinc salts and/ororganic acid alkaline earth metal salts in view of anti-coloration, heatresistance, and cost.

The polyols include trimethylolpropane, ditrimethylolpropane,pentaerythritol, dipentaerythritol, polypentaerythritol, a stearic acidhalf ester with pentaerythritol or dipentaerythritol,bis(dipentaerythritol) adipate, glycerol,tris(2-hydroxyethyl)isocyanurate, sorbitol, mannitol, and trehalose.

The epoxy compounds include epoxidized animal or vegetable oils, such asepoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil,epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil,and epoxidized safflower oil; epoxidized methyl stearate, epoxidizedbutyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearylstearate, epoxidized polybutadiene, tris(epoxypropyl)isocyanurate,epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acidester, vinylcyclohexene diepoxide, dicyclohexene diepoxide,3,4-epoxycyclohexene methyl epoxycyclohexanecarboxylate, bisphenol Adiglycidyl ether, trimethylolpropane polyglycidyl ether, glycerolpolyglycidyl ether, hexanediol polyglycidyl ether,2,2-dimethyl-1,3-propanediol polyglycidyl ether, hydrogenated bisphenolpolyglycidyl ether, and cyclohexanedimethanol polyglycidyl ether.

The organic phosphite compounds include triphenyl phosphite,tris(2,4-di-t-butylphenyl)phosphite,tris(2,5-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite,tris(dinonylphenyl)phosphite, tris(mono/di-mixed nonylphenyl)phosphite,diphenyl acid phosphite, 2,2′-methylenebis(4,6-di-t-butylphenyl)octylphosphite, diphenyldecyl phosphite, diphenyloctyl phosphite,di(nonylphenyl)pentaerythritol diphosphite, phenyldiisodecyl phosphite,tributyl phosphite, tris(2-ethylhexyl)phosphite, tridecyl phosphite,trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite,trilauryl trithiophosphite, bis(neopentylglycol).1,4-cyclohexanedimethyl diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,5-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-methylphenyl)penta-erythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,distearyl-pentaerythritol diphosphite, tetra(C12-15 mixedalkyl)-4,4′-isopropylidenediphenyl phosphite,bis[2,2′-methylenebis(4,6-diamylphenyl)].isopropylidenediphenylphosphite,tetratridecyl.4,4′-butylidenebis(2-t-butyl-5-methylphenol)diphosphite,hexa(tridecyl).1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane.triphosphite,tetrakis(2,4-di-t-butylphenyl)biphenylene diphosphonite,tris(2-[(2,4,7,9-tetrakis-t-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine,9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide, and2-butyl-2-ethylpropanediol.2,4,6-tri-t-butylphenol monophosphite.

The phenol antioxidants include 2,6-di-t-butyl-p-cresol,2,6-diphenyl-4-octadecyloxyphenol,stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate,distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, tridecyl3,5-di-t-butyl-4-hydroxybenzyl-thioacetate,thiodiethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate],4,4′-thiobis(6-t-butyl-m-cresol),2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine,2,2′-methylenebis(4-methyl-6-t-butylphenol),bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid]glycol ester,4,4′-butylidenebis(2,6-di-t-butylphenol),4,4′-butylidenebis(6-t-butyl-3-methylphenol),2,2′-ethylidenebis(4,6-di-t-butylphenol),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terephthalate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate,1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol,3,9-bis[2-(3-t-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,and triethylene glycolbis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate].

The sulfur antioxidants include dialkyl thiodipropionates, such as adilauryl, dimyristyl, myristylstearyl or distearyl ester ofthiodipropionic acid; and polyol β-alkylmercaptopropionic acid esters,such as pentaerythritol tetra(β-dodecylmercaptopropionate).

The ultraviolet absorbers include 2-hydroxybenzophenones, such as2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octyloxybenzophenone,2-hydroxy-4-t-butyl-4′-(2-methacryloyloxyethoxyethoxy)benzophenone, and5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone);2-(2-hydroxyphenyl)benzotriazoles, such as2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-t-octylphenyl)benzotriazole,2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3-dodecyl-5-methylphenyl)benzotriazole,2-(2-hydroxy-3-t-butyl-5-C7-9 mixed alkoxycarbonylethylphenyl)triazole,2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole,2,2′-methylenebis(4-t-octyl-6-benzotriazolylphenol), and2-(2-hydroxy-3-t-butyl-5-carboxyphenyl)benzotriazole polyethylene glycolester; 2-(2-hydroxyphenyl)-1,3,5-triazines, such as2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,and2-(2-hydroxy-4-acryloyloxyethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;benzoates, such as phenyl salicylate, resorcinol monobenzoate,2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate,2,4-di-t-amylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, and hexadecyl3,5-di-t-butyl-4-hydroxybenzoate; substituted oxanilides, such as2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; andcyanoacrylates, such as ethyl α-cyano-β,β-diphenylacrylate and methyl2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate.

The hindered amine light stabilizers include2,2,6,6-tetramethyl-4-piperidyl stearate,1,2,2,6,6-pentamethyl-4-piperidyl stearate,2,2,6,6-tetramethyl-4-piperidyl benzoate,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,bis(2,2,6,6-tetramethyl-4-piperidyl).bis(tridecyl)-1,2,3,4-butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-piperidyl).bis(tridecyl)-1,2,3,4-butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-t-butyl-4-hydroxybenzyl)malonate,1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinatepolycondensate,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethanepolycondensate,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazinepolycondensate,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-t-octylamino-s-triazinepolycondensate,1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane,1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane,1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino-s-triazin-6-ylamino]undecane,1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino-s-triazin-6-ylamino]undecane,3,9-bis[1,1-dimethyl-2-[tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,and3,9-bis[1,1-dimethyl-2-[tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

The inorganic stabilizers include hydrotalcite, calcium phosphate,calcium oxide, calcium hydroxide, calcium silicate, magnesium phosphate,magnesium oxide, magnesium hydroxide, aluminum hydroxide,non-crystalline aluminosilicates, alkali metal and/or alkaline earthmetal aluminosilicates having a zeolite crystal structure, silicapowders, overbased calcium carbonate, sodium perchlorate, magnesiumperchlorate, and barium perchlorate.

Hydrotalcite recited above is a complex salt compound composed of (i)magnesium and/or an alkali metal and aluminum or (ii) zinc, magnesium,and aluminum as represented by formula (I) shown below, of which thewater of crystallization may be removed.Mg_(x1)Zn_(x2)Al₂(OH)_(2(x1+x2)+4)(CO₃)_(1/2).mH₂O   (I)wherein x1 and x2 each represent a number satisfying formulae:0≦x2/x1<10 and 2≦x1+x2≦20; and m represents 0 or a positive number.

The hydrotalcite may be coated with a higher fatty acid, e.g., stearicacid, a higher fatty acid metal salt, e.g., an alkali metal oleate, anorganic sulfonic acid metal salt, e.g., an alkali metaldodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acidester, a wax, etc.

The hydrotalcite may be either a naturally occurring product or asynthetic product. Hydrotalcite can be synthesized by known processesdescribed, e.g., in JP-B-46-2280, JP-B-50-30039, JP-B-51-29129,JP-B-3-36839, JP-A-61-174270, and JP-A-5-179052. Any hydrotalcitespecies can be used with no limitation on crystal structure, crystalgrain size, and the like.

The fillers include calcium carbonate, silica, clay, glass beads, mica,sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF,gypsum whisker, xonotlite, MOS, phosphate fiber, glass fiber, carbonfiber, and aramid fiber.

The antifogging agents include polyoxyethylene lauryl ether,polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether,polyethylene glycol monopalmitate, polyethylene glycol monostearate,polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, glycerol monolaurate, glycerol monopalmitate, glycerolmonostearate, glycerol monooleate, pentaerythritol monolaurate, sorbitanmonopalmitate, sorbitan monobehenate, sorbitan distearate, diglyceroldioleate sodium laurylsulfate, sodium dodecylbenzenesulfonate, sodiumbutylnaphthalenesulfonate, cetyltrimethylammonium chloride, dodecylaminehydrochloride, lauric acid laurylamidoethyl phosphate,triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, anddodecylpyridinium salts.

The anti-misting agents include fluorine-containing compounds, such asanionic fluorine-containing surfactants, cationic fluorine-containingsurfactants, amphoteric fluorine-containing surfactants, nonionicfluorine-containing surfactants, and fluorine-containing oligomers.

The stabilization assistants include diphenylthiourea, diphenylurea,anilinodithiotriazine, melamine, benzoic acid, cinnamic acid,p-tert-butylbenzoic acid, and aliphatic organic acids.

The organotin compounds include a dilaurate, a dimaleate, a dimercaptideor a maleate polymer of dibutyltin or dioctyltin.

In addition to the above-described components, the resin composition canfurther contain other additives according to necessity. Usable otheradditives include those commonly added to chlorine-containing resins,such as crosslinking agents, antistatics, thixotropic agents,anti-plate-out agents, surface treating agents, lubricants, flameretardants, fluorescent agents, antifungal agents, antibacterial agents,metal deactivators, parting agents, pigments, processing aids,antioxidants, light stabilizers, and blowing agents.

The chlorine-containing resin composition of the present invention cancontain the other additives in an amount usually up to 100 parts by massper 100 parts by mass of the chlorine-containing resin.

The chlorine-containing resin composition of the invention that containsthe polyethylene plasticizer of the invention is useful asconstructional materials, such as wall materials, floor materials,window frames, and wall paper; wire covering materials; automotiveinterior or exterior materials; agricultural materials, such ashothouses and tunnels; food (e.g., fishes) packaging materials, such aswraps and trays; coatings; and other miscellaneous goods, such as hoses,pipes, sheets, toys, gloves, and so forth.

The present invention will now be illustrated in greater detail withreference to Preparation Examples and Examples, but it should beunderstood that the invention is not construed as being limited thereto.

Preparation Examples 1 to 3 hereinafter given are to show examples ofthe polyester plasticizers of the present invention, and Examples 1 to 3hereinafter given are to demonstrate examples of the chlorine-containingresin composition of the present invention which contains the polyesterplasticizer of the present invention obtained in Preparation Examples 1to 3. Comparative Preparation Examples 1 to 2 hereinafter described areto show polyester plasticizers synthesized without using3-methyl-1,5-pentanediol. Comparative Examples 1 and 2 are intended toshow chlorine-containing resin compositions containing the polyesterplasticizers obtained in Comparative Preparation Examples 1 and 2.

PREPARATION EXAMPLE 1

In a reaction flask were put 1.7 molar parts of2-methyl-1,3-propanediol, 1.2 molar parts of 3-methyl-1,5-pentanediol,3.0 molar parts of adipic acid, 1.1 molar parts of isononanol, and0.0005 molar parts of titanium tetraisopropoxide and allowed to react at220° C. in a nitrogen stream for 8 hours while removing produced waterby evaporation and then under a pressure of 4000 Pa at 220° C. for 1hour to give polyester plasticizer No. 1, which was found to have anaverage molecular weight of 1800 and a viscosity of 3000 mPa.s.

PREPARATION EXAMPLE 2

In a reaction flask were put 1.7 molar parts of2-methyl-1,3-propanediol, 0.6 molar parts of 3-methyl-1,5-pentanediol,0.6 molar parts of neopentyl glycol, 3.0 molar parts of adipic acid, 1.2molar parts of 2-ethylhexanol, and 0.0005 molar parts of titaniumtetraisopropoxide and allowed to react at 220° C. in a nitrogen streamfor 8 hours while removing produced water by evaporation and then undera pressure of 4000 Pa at 220° C. for 1 hour to give polyesterplasticizer No. 2 having an average molecular weight of 1700 and aviscosity of 3000 mPa.s.

PREPARATION EXAMPLE 3

In a reaction flask were put 1.8 molar parts of2-methyl-1,3-propanediol, 0.6 molar parts of 3-methyl-1,5-pentanediol,0.6 molar parts of neopentyl glycol, 3.0 molar parts of adipic acid, 0.3molar parts of 12-hydroxystearic acid, 1.2 molar parts of2-ethylhexanol, and 0.0005 molar parts of titanium tetraisopropoxide andallowed to react at 220° C. in a nitrogen stream for 8 hours whileremoving produced water by evaporation and then under a pressure of 4000Pa for 1 hour to give polyester plasticizer No. 3 having an averagemolecular weight of 1900 and a viscosity of 3000 mPa.s.

COMPARATIVE PREPARATION EXAMPLE 1

In a reaction flask were put 2.9 molar parts of2-methyl-1,3-propanediol, 3.0 molar parts of adipic acid, 1.1 molarparts of isononanol, and 0.0005 molar parts of titaniumtetraisopropoxide and allowed to react at 220° C. in a nitrogen streamfor 8 hours while removing produced water by evaporation and then undera pressure of 4000 Pa at 220° C. for 1 hour to give polyesterplasticizer No. 4 having an average molecular weight of 1600 and aviscosity of 3000 mPa.s.

COMPARATIVE PREPARATION EXAMPLE 2

In a reaction flask were put 1.7 molar parts of2-methyl-1,3-propanediol, 1.2 molar parts of neopentyl glycol, 3.0 molarparts of adipic acid, 1.1 molar parts of 2-ethylhexanol, and 0.0005molar parts of titanium tetraisopropoxide and allowed to react at 220°C. in a nitrogen stream for 8 hours while removing produced water byevaporation and then under a pressure of 4000 Pa at 220° C. for 1 hourto give polyester plasticizer No. 5 having an average molecular weightof 1700 and a viscosity of 3000 mPa.s.

EXAMPLES 1 TO 3

Components shown in the following formulation, including each of thepolyester plasticizer Nos. 1 to 3 obtained in Preparation Examples 1 to3, were compounded into a chlorine-containing resin composition, whichwas kneaded on rolls at 170° C. at 30 rpm for 7 minutes. The compoundwas pressed at 180° C. for 5 minutes to prepare a 1 mm thick sheet. Thesheet was evaluated by a tensile test (JIS K71132) and an oil resistancetest (ASTM-No. 2, oil; 100° C., 96 hrs). The test results are shown inTable 1.

Formulation (Unit: Part by Weight): Polyvinyl chloride resin (degree of100 polymerization: 1050) Polyester plasticizer (see Table 1) 50Epoxidized soybean oil 2 Adekastab 1500 (phosphite compound 0.5available from Asahi Denka Co., Ltd.) 2-Ethylhexanoic acid 0.02 Bariumcarbonate 0.2 Zinc p-tert-butylbenzoate 0.05 Zinc m-toluylate 0.05Barium stearate 1 Zinc stearate 0.4 Hydrotalcite (DHT-4A available from0.4 Kyowa Chemical Industry Co., Ltd.) Dibenzoylmethane 0.1 Bisphenol A0.14

COMPARATIVE EXAMPLES 1 AND 2

A sheet was prepared in the same manner as in Example 1, except forusing each of polyester plasticizer Nos. 4 and 5 obtained in ComparativePreparation Examples 1 and 2 as a polyester plasticizer. The sheet wasevaluated by a tensile test and an oil resistance test in the samemanner as in Example 1. The test results obtained are shown in Table 1.TABLE 1 Oil Resistance Test Tensile Test Tensile 100% Tensile ElongationStrength Polyester Modulus Elongation Strength Retention RetentionPlasticizer (MPa) (%) (MPa) (%) (%) Ex. 1 No. 1 11.5 370 22.8 99 105 Ex.2 No. 2 12.0 360 23.0 99 110 Ex. 3 No. 3 11.8 362 23.3 100 105 Comp. Ex.1 No. 4 13.9 348 25.1 94 95 Comp. Ex. 2 No. 5 13.3 322 24.6 86 86

As is apparent from the results in Table 1, the resin compoundcontaining the polyester plasticizer of the present invention exhibits alower 100% modulus and a higher elongation than those containing theequal amount of the polyethylene plasticizer synthesized without using3-methyl-1,5-pentanediol while retaining sufficient tensile strength.Thus, the polyester plasticizer according to the present invention hasnow proved to achieve excellent plasticization efficiency. It has alsobeen confirmed that the chlorine-containing resin composition containingthe polyester plasticizer of the invention exhibits satisfactoryretention percentage in elongation and tensile strength in the oilresistance test, proving excellent in oil resistance.

INDUSTRIAL APPLICABILITY

The polyester plasticizer according to the present invention exhibitshigh plasticization efficiency and imparts excellent oil resistance tosynthetic resins, particularly chlorine-containing resins.

1. A polyester plasticizer having an average molecular weight of 500 to5000 which is obtained by the reaction of (a) a diol componentcomprising 100 molar parts of 2-methyl-1,3-propanediol, 10 to 1000 molarparts of 3-methyl-1,5-pentanediol, and 0 to 1000 molar parts of anadditional aliphatic diol, (b) an organic dicarboxylic acid componentcomprising 100 molar parts of adipic acid and 0 to 100 molar parts of anadditional organic dicarboxylic acid, and (c) a chain terminatorcomprising a monovalent aliphatic alcohol or a monovalent aliphaticorganic acid.
 2. The polyester plasticizer according to claim 1, whereinthe amount of 3-methyl-1,5-pentanediol is 20 to 100 molar parts, and theamount of the additional aliphatic diol is 0 to 200 molar parts.
 3. Thepolyester plasticizer according to claim 1, which has an averagemolecular weight of 1000 to
 3000. 4. A chlorine-containing resincomposition comprising 100 parts by mass of a chlorine-containing resin,10 to 100 parts by mass of the polyester plasticizer according to claim1, and 0 to 100 parts by mass of an additive.